Silver halide photographic material containing imidazopyrazole type coupler and image forming method using said coupler

ABSTRACT

An image forming method is disclosed which comprises developing a silver halide photographic material with a developing solution containing an aromatic primary amine developing agent in the presence of an imidazo[1,2-b]pyrazole type coupler represented by the following general formula (I): ##STR1## wherein R 1  represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group or an aryl group; R 2  represents an alkoxy group, an aryloxy group or an amino group; R 3  represents a hydrogen atom, an alkyl group or an aryl group; and X represents a hydrogen atom or a group capable of being released upon coupling with an oxidation product of an aromatic primary amine developing agent. 
     The magenta coupler represented by general formula (I) is excellent in color reproducibility, sensitivity and color density. 
     A silver halide color photographic material containing the magenta coupler is also disclosed.

FIELD OF THE INVENTION

The present invention relates to a silver halide photographic materialand an image forming method, and more particularly to a silver halidephotographic material containing a novel imidazopyrazole type couplerhaving an improved color forming property and an image forming methodusing the coupler.

BACKGROUND OF THE INVENTION

It is well known that an aromatic primary amine color developing agentoxidized by exposed silver halide as an oxidizing agent reacts with acoupler to form a color image.

Magenta color image forming couplers which have been widely used inpractice and on which various investigations have been made are almostalways 5-pyrazolones. However, it is known that dyes formed from5-pyrazolone type couplers have an undesirable absorption of the yellowcomponent in the region around 430 nm, which causes color turbidity.

In order to reduce the yellow component absorption, apyrazolobenzimidazole nucleus as described in British Patent 1,047,612,an indazolone nucleus as described in U.S. Pat. No. 3,770,447, apyrazolo[5,1-c]-1,2,4-triazole nucleus as described in U.S. Pat. No.3,725,067, a pyrazolo[1,5-b]-1,2,4-triazole nucleus as described inJP-A-59-171956 (the term "JP-A" as used herein means an "unexaminedpublished Japanese patent application") and U.S. Pat. No. 4,540,654 andan imidazo[1,2-b]pyrazole nucleus as described in JP-A-59-162548 andU.S. Pat. No. 4,500,630 have been proposed as a magenta color imageforming coupler skeleton.

Among them, pyrazolo[5,1-c]-1,2,4-triazole type magenta couplers andpyrazolo[1,5-b]-1,2,4-triazole type magenta couplers (both types ofcouplers are generally referred to as pyrazolotriazole type couplershereinafter) are particularly useful and have been practically employedin some silver halide color photographic materials.

Dyes formed from the pyrazolotriazole type couplers are superior tothose formed from conventional 5-pyrazolones in view of the undesirableabsorption of the yellow component and they are also preferred from astandpoint of color reproduction since their absorption spectra sharplydecrease to zero on the longer wavelength side.

The inventors have found, however, that these pyrazolotriazole typecouplers have the undesirable properties described below, although theyhave the above described excellent properties. When these couplers areused together with silver halide, which acts as an oxidizing agent foran aromatic primary amine developing agent necessary for a color formingreaction, and more specifically, when an emulsified dispersion of thecouplers and a silver halide emulsion are mixed to form a coating andits photographic characteristics are evaluated, the silver halideemulsion does not have its original sensitivity, gradation or fog, andas a result the sensitivity may increase or decrease depending on theemulsion used and the resulting color density decreases. Such facts canbe determined by a comparison of these results with those obtained bycolor development or black and white development of a coating preparedby incorporating a 5-pyrazolone type coupler under the same conditions.Also, some of these facts can be confirmed by a comparison with thoseresults obtained by black and white development of a coating containingonly the silver halide emulsion.

It is not essentially expected that the couplers used in silver halidecolor photographic materials have any effect on the silver halideemulsions used except for couplers having a specific function such asdevelopment inhibitor releasing couplers or developing acceleratorreleasing couplers. Particularly, it is undesirable to have an effect ona light sensitive process and cause sensitization or desensitization.With recent silver halide photographic materials in which rapidprocessing capability is required, it is strongly desired not toinfluence the silver halide emulsion.

The inventors have confirmed that pyrazolotriazole type couplers havestronger interaction with silver ion or silver halide in comparison withcompounds having a 5-pyrazolone residue which have hitherto been widelyused as magenta couplers, specifically to effect the formation ofcomplex or adsorption. Further, it has been confirmed that such aninteraction causes desensitization of the emulsion and a decrease incolor reproduction.

The inventors have determined that the undesirable interaction of apyrazolotriazole type coupler with silver is difficult to control andturned his attention to an imidazopyrazole nucleus for solving theproblem. However, dyes formed from compounds having an imidazopyrazolenucleus are apt to have their spectral absorption in a shorter wavelength region as compared with those formed from pyrazolotriazole typecouplers and they are not preferred in view of color reproduction.

SUMMARY OF THE INVENTION

Therefore, one object of the present invention is to provide a novelcoupler which does not cause an interaction with silver halide likepyrazolotriazole type couplers but which has excellent colorreproducibility like pyrazolotriazole type couplers.

Another object of the present invention is to provide an image formingmethod which results in excellent color reproducibility, sensitivity andcolor density.

A further object of the present invention is to provide a silver halidecolor photographic material which results in excellent colorreproducibility, sensitivity and color density.

Other objects of the present invention will become apparent from thefollowing description and examples.

As a result of intensive investigations, the inventors have found thatimidazopyrazole compounds having a specific substituent on their nucleido not suffer from the undesirable interaction with silver which isobserved with pyrazolotriazole type couplers. The inventors have alsofound that the present invention can exhibit excellent colorreproducibility, sensitivity and color density.

The present invention also relates to an image forming method, whichcomprises developing a silver halide photographic material with adeveloping solution containing an aromatic primary amine developingagent in the presence of an imidazo[1,2b]pyrazole type couplerrepresented by the following general formula (I): ##STR2## wherein R₁represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxygroup or an aryl group; R₂ represents an alkoxy group, an aryloxy groupor an amino group; R₃ represents a hydrogen atom, an alkyl group or anaryl group; and X represents a hydrogen atom or a group capable of beingreleased upon coupling with an oxidation product of an aromatic primaryamine developing agent.

Also, the present invention is directed to a silver halide colorphotographic material comprising a support having thereon at least onelayer containing the magenta coupler represented by the general formula(I) described above.

BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWING

FIG. 1 is a graph showing the absorption spectra of azomethine dyesobtained from the coupler according to the present invention and from acomparative coupler, respectively.

DETAILED DESCRIPTION OF THE INVENTION

The substituents represented by R₁, R₂, R₃ and X in general formula (I)will be explained in detail below.

R₁ represents a hydrogen atom, an alkyl group, an alkoxy group, anaryloxy group or an aryl group. Also, R₁ is a substituent having theHammett's σ_(p) value of not more than 0.1, preferably from -0.5 to0.05, and more preferably from -0.20 to 0.03.

The Hammett's rule is an empirical rule which was proposed by L. P.Hammett in 1935 in order to quantitatively examine the effect of asubstituent on a reaction or equilibrium of a benzene derivative and itsuse is widely recognized at present.

The substituent constants obtained by the Hammett's rule include σpvalues and σm values and these values are described in detail in manyreferences, for example, J. A. Dean (Ed.) Lange's Handbook of Chemistry,12th Edition (McGraw Hill, 1979) and Kagaku no Ryoiki Zokan, Vol. 122,pages 96 to 103 (Nankodo, 1979).

In the present invention, a substituent on the aryl group represented byR₁ is defined by the substituent constant σp value. It should be notedthat the substituents are not limited to those having their known valuedescribed in references, and include substituents having the Hammett'ssubstituent constant σp value within the above described range whendetermined based on the Hammett's rule, even if the values of thesubstituents are not described in references.

The σp values of representative substituents are shown below.

    ______________________________________                                        --NHCH.sub.3                                                                            -0.84        --N(CH.sub.3).sub.2                                                                     -0.83                                        --OCH.sub.3                                                                             -0.32        --C(CH.sub.3).sub.3                                                                     -0.20                                        --CH.sub.3                                                                              -0.17        --C.sub.6 H.sub.5                                                                       0.01                                         ______________________________________                                    

When the σp value exceeds 0.1, the coupling activity of the couplertends to decrease and problems occur mainly in sensitivity and colordensity that is produced. On the other hand, when the σp value is lessthan -0.5, the absorption spectrum of an azomethine dye formed ispresent in a short wavelength region and its hue is not suitable as agood magenta dye, resulting in a problem in color reproduction.

The alkyl group includes a substituted or unsubstituted, straight chainor branched chain alkyl group, and is preferably a substituted orunsubstituted, straight chain or branched chain alkyl group having from1 to 32 carbon atoms.

The substituent which may present in the alkyl group includes a groupbonded through an oxygen atom, a nitrogen atom, a sulfur atom or acarbonyl group, an alkyl group, an aryl group, a heterocyclic group, acyano group, and a halogen atom. The group bonded through an oxygenatom, a nitrogen atom, a sulfur atom or a carbonyl group includes ahydroxy group, an amino group, a nitro group, a carboxy group, an acylgroup, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoylgroup, an alkoxy group, an aryloxy group, a heterocyclic oxy group, anacyloxy group, a carbamoyloxy group, a silyloxy group, anaryloxycarbonylamino group, an acylamino group, an anilino group, analkylamino group, a ureido group, a sulfamoylamino group, analkoxycarbonylamino group, a sulfonamido group, an imido group, analkylthio group, an arylthio group, a heterocyclic thio group, asulfamoyl group, a sulfonyl group or a sulfinyl group.

The alkoxy group includes a group composed of a substituted orunsubstituted, straight chain or branched chain alkyl group bonded to anoxygen atom, and is preferably a group composed of a substituted orunsubstituted, straight chain or branched chain alkyl group having from1 to 32 carbon atoms bonded to an oxygen atom. The alkyl moiety of thealkoxy group may have further substituents selected from those describedfor the above alkyl group.

The aryloxy group includes an unsubstituted or substituted aryloxy groupand the substituents may include those described above for the alkylgroup. The preferred aryloxy group includes an unsubstituted phenoxy ornaphthyloxy group and a phenoxy or naphthyloxy group substituted withthe substituents selected from those described above for the alkylgroup.

Specific examples of the more preferred aryloxy group include a phenoxygroup, a 2-methylphenoxy group, a 4-tert-butylphenoxy group, a3-nitrophenoxy group, a 3-tert-butyloxycarbamoylphenoxy group, a3-methoxycarbamoylphenoxy group, a 1-naphthyloxy group and a2-naphthyloxy group.

The aryl group includes an unsubstituted aryl group and an aryl groupsubstituted with one or more substituents, which may be the same ordifferent, each having the Hammett's σp value of not more than 0.Preferred examples of the aryl group include an unsubstituted phenyl ornaphthyl group and a phenyl or naphthyl group substituted with one ormore substituents, which may be the same or different, each having theHammett's σp value of not more than 0 such as an alkyl group, an arylgroup, an alkoxy group, an aryloxy group, an acylamino group, a urethanegroup or a ureido group. Specific examples of more preferred aryl groupsinclude a phenyl group, a 2,4,6-trimethylphenyl group, a1-tert-butylphenyl group, an o-aminophenyl group, an o-methoxyphenylgroup, a p-dimethylaminophenyl group, an m-methoxymethylphenyl group, anm-methoxyethoxyphenyl group, a p-trimethylsilylphenyl group, a1-naphthyl group and a 2-naphthyl group.

R₁ preferably represents an alkyl group, an aryloxy group or an alkoxygroup, and more preferably an alkyl group or an aryloxy group.

R₂ represents an alkoxy group, an aryloxy group or an amino group.

The alkoxy group and aryloxy group each has the same meaning asdescribed above.

The amino group includes an unsubstituted or substituted amino grouprepresented by the following formula: ##STR3## wherein R' and R", whichmay be the same or different, each represents a hydrogen atom, an alkylgroup or an aryl group, or R' and R" may combine with each other to forma ring.

The alkyl group represented by R' or R" has the same meaning asdescribed above. The aryl group represented by R' or R" includes anunsubstituted aryl group and an aryl group substituted with one or moresubstituents selected from those described above for the alkyl group.

Among the amino groups represented by the above formula,, those whereineither R' or R" or both each represents an unsubstituted or substituted,straight chain or branched chain alkyl group having from 1 to 32 carbonatoms are preferred.

R₂ preferably. represents an alkoxy group or a substituted amino group,and more preferably an alkoxy group or an N,N-substituted amino group.

R₃ represents a hydrogen atom, an alkyl group or an aryl group. Thealkyl group has the same meaning as described above. The aryl group isunsubstituted or substituted group, in which one or more positions aresubstituted by the same substituents as defined above for the alkylgroup.

R₃ preferably represents an alkyl group or an aryl group. As for alkylgroup, an unsubstituted or substituted, straight chain or branched chainalkyl group having from 1 to 32 carbon atoms is preferred. As for arylgroup, an ortho-substituted aryl group is preferred andortho-disubstituted aryl group is more preferred.

X represents a hydrogen atom, a halogen atom (for example, fluorine,chlorine, bromine, or iodine), a carboxy group, a group bonded to thecoupling position through an oxygen atom (for example, acetoxy,propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyoxaloyloxy,vinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenoxyl,4-methanesulfonamidophenoxy, 4-methanesulfonylphenoxy, α-naphthoxy,3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy,benzyloxy, 2-phenetyloxy, 2-phenoxyethoxy, 5-phenyltetrazolyloxy, or2-benzothiazolyloxy), a group bonded to the coupling position through anitrogen atom (for example, benzenesulfonamido,N-ethyltoluenesulfonamido, heptafluorobutanamido,2,3,4,5,6-pentafluorobenzamido, octanesulfonamido, p-cyanophenylureido,N,N-diethylsulfamoylamino, 1-piperidyl,5,5-dimethyl-2,4-dioxo-3-oxazolidinyl, 1-benzyl-5-ethoxy-3-hydantoinyl,2N-1,1-dioxo-3(2H)-oxo-1,2-benzosothiazolyl,2-oxo-1,2-dihydro-1-pyridinyl, imidazolyl, pyrazolyl,3,5-diethyl-1,2,4-triazol-1-yl, 5- or 6-bromobenzotriazol-1-yl,5-methyl-1,2,3,4-tetrazol-1-yl, or benzimidazolyl) , or a group bondedto the coupling position through a sulfur atom (for example, phenylthio,2-carboxyphenylthio, 2-methoxy-5-tert-octylphenylthio,4-methanesulfonylphenylthio, 4-octanesulfonamidophenylthio, benzylthio,2-cyanoethylthio, 1-ethoxycarbonyltridecylthio,5-phenyl-2,3,4,5-tetrazolylthio, or 2-benzothiazolyl).

X preferably represents a halogen atom or a group bonded through asulfur atom.

Also, R₁, R₂, R₃ or X may be a divalent group to form a bis group.

When the moiety represented by general formula (I) is included in avinyl monomer, the vinyl group may further have a substituent inaddition to the coupler moiety represented by general formula (I).Preferred examples of such a substituent include a hydrogen atom, achlorine atom or a lower alkyl group having from 1 to 4 carbon atoms(for example, methyl, or ethyl).

The monomers including the coupler moiety represented by general formula(I) may form a copolymer together with non-color forming ethylenicmonomers which do not undergo coupling with the oxidation products ofaromatic primary amine developing agents.

Examples of the non-color forming ethylenic monomers which do not couplewith the oxidation products of aromatic primary amine developing agentsinclude an acrylic acid (for example, acrylic acid, α-chloroacrylicacid, or an a-alkylacrylic acid such as methacrylic acid), an ester oran amide derived from an acrylic acid (for example, acrylamide,n-butylacrylamide, tert-butylacrylamide, diacetoneacrylamide,methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate,n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, 2-ethylhexylacrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethylmethacrylate, n-butyl methacrylate, or β-hydroxy methacrylate),methylene di-bisacrylamide, a vinyl ester (for example, vinyl acetate,vinyl propionate, or vinyl laurate), acrylonitrile, methacrylonitrile,an aromatic vinyl compound (for example, styrene and a derivativethereof, for example, vinyl toluene, divinyl benzene, vinylacetophenone, or sulfostyrene), itaconic acid, citraconic acid, crotonicacid, vinylidene chloride, a vinyl alkyl ether (for example, vinyl ethylether), maleic acid, maleic anhydride, an ester of maleic acid,N-vinyl-2-pyrrolidone, N-vinyl pyridine, and 2- or 4-vinyl pyridine. Twoor more non-color forming ethylenically unsaturated monomers describedabove can be used together. For example, a combination of n-butylacrylate and methyl acrylate, styrene and methacrylic acid, methacrylicacid and acrylamide, or methyl methacrylate and diacetoneacrylamide canbe employed.

The non-color forming ethylenically unsaturated monomer which is used tocopolymerize with a solid water-insoluble monomer coupler can beselected so that the copolymer to be formed possesses good physicalproperties and/or chemical properties, for example, solubility,compatibility with a binder such as gelatin in a photographic colloidcomposition, flexibility, heat stability, etc., as well known in thefield of polymer color couplers.

Polymer couplers which can be used in the present invention may bewater-soluble couplers or water-insoluble couplers. Particularly,polymer couplers in the form of a latex are preferably used.

The coupler represented by general formula (I) according to the presentinvention can be employed by incorporating into a light-sensitivematerial or a developing solution. The amount of the coupler ispreferably from 1×10³ to 1 mol per mol of silver, more preferably from1×10⁻¹ to 1 mol per mol of silver in the case of using said coupler in alight-sensitive material, and when using said coupler in a developingsolution, it is preferably from 1 to 6 g per liter, more preferably from2 to 3 g per liter of the developing solution.

Specific examples of the representative magenta couplers (1) to (41)according to the present invention are set forth below, but the presentinvention should not be construed as being limited thereto. ##STR4##

A method for the synthesis of the coupler according to the presentinvention is described below. A general method for the synthesis of thecoupler of the invention can be illustrated by the following reactionscheme: ##STR5## wherein R₁, R₂, R₃ and X each has the same meaning asdefined above; and L represents a group capable of being released, forexample, a halogen atom, a nitro group, a sulfinyl group or a sulfonylgroup.

The method for the synthesis of the coupler of the invention isspecifically described with reference to the following synthesisexamples.

SYNTHESIS EXAMPLE 1 Synthesis of Coupler (5) ##STR6##

2.76 g (0.02 mol) of 5-amino-4-chloro-3-methylpyrazole (Compound 1) wasdissolved in 10 ml of chloroform, the resulting solution was heated to400° C. and 1.4 ml (0.01 mol) of ethyl α-bromopyruvate was added theretowhile stirring. The mixture was stirred for one day at room temperature.The crystals thus deposited were collected and washed with chloroformand then washed with a mixture of acetonitrile and water (1:1 by volume)to obtain 1.02 g (45%) of Coupler (5).

SYNTHESIS EXAMPLE 2 Synthesis of Coupler (7) ##STR7##

4.55 g of Coupler (5) was dissolved in 100 ml of ethylene glycol and tothe resulting solution 4.89 g of potassium tert-butoxide was added. Themixture was then heated at 50° C. while stirring for 7 hours. Thereaction solution was neutralized by adding dilute hydrochloric acid andextracted three times with ethyl acetate. The extract was dried withmagnesium sulfate and concentrated. The solid thus obtained wasrecrystallized from acetonitrile to obtain 4.45 g (91% yield) ofCompound 3 in total.

2.44 g of Compound 3 was dissolved in 10 ml of N,N-dimethylacetamide andacid chloride was gradually added dropwise to the resulting solution andthen 1.62 ml of pyridine was added, followed by stirring at roomtemperature for 1.5 hours. The reaction mixture was extracted threetimes with ethyl acetate. The extract was washed twice with a saturatedaqueous solution of sodium chloride, dried with magnesium sulfate andconcentrated to obtain 11.63 g of a viscous oily product. The productwas purified by silica gel column chromatography (hexane and ethylacetate =6:1 by volume) to obtain 5.86 g (97% yield) of Coupler (7).

The imidazopyrazole type couplers according to the present invention donot have the undesirable interaction with silver which is observed withpyrazolotriazole type couplers, and as a result they are excellentcouplers having good color reproducibility, sensitivity and colordensity.

By using the couplers according to the present invention, it is possibleto design silver halide color photographic materials having sufficientlyhigh sensitivity, gradation and color density even upon rapidprocessing.

The present invention is explained in greater detail with reference tothe following example, but the present invention should not be construedas being limited thereto.

EXAMPLE 1

1.0 mmol of Coupler (5) or (7) according to the present invention orComparative Coupler (M-1) shown below was dissolved in 10 ml of ethanol.1.2 mmol of4-[N-ethyl-N-(2-methanesulfonamidoethyl)]amino-2-methylaniline monosulfate as a color developing agent was added to each of the resultingsolutions and then a solution containing 12.0 mmol of anhydrous sodiumcarbonate dissolved in 5 ml of water was added thereto, followed bystirring at room temperature. A solution containing 1.2 mmol ofpotassium persulfate dissolved in 10 ml of water was gradually addeddropwise to the mixture. After thoroughly stirring at room temperaturefor one hour, the mixture was extracted by adding 50 ml of ethyl acetateand 30 ml of water. The ethyl acetate layer was thoroughly washed with asaturated aqueous solution of sodium chloride, and the solvent wasremoved. The residue was purified by silica gel column chromatography.

The resulting azomethine dye of Coupler (5) or (7) according to thepresent invention or Comparative Coupler (M-1) was measured to determineits absorption spectrum in ethyl acetate.

The results are shown in FIG. 1. ##STR8##

The absorption characteristics of each dye are also shown in Table 1below. As can be seen from these results, the dye formed from thecoupler according to the present invention has a sharply decreasingabsorption on the longer wavelength side and a small subsidiaryabsorption around 400 to 450 nm in comparison with a conventionalpyrazolone magenta coupler and is advantageous in view of forming colorimages.

                  TABLE 1                                                         ______________________________________                                                  Absorption Maximum                                                            Wavelength      Half-Width                                          Coupler   (λ EtOAc max)                                                                          (Δ1/2)                                                                            S.sub.+60 *                               ______________________________________                                        Comparative                                                                             526.3 nm        65.2 nm   0.117                                     Coupler (M-1)                                                                 Coupler (5)                                                                             526.1 nm        67.1 nm   0.047                                     Coupler (7)                                                                             529.5 nm        66.4 nm   0.061                                     ______________________________________                                         *S.sub.+60 means a ratio of absorbance at a point of the absorption           maximum plus 60 nm to absorbance at the absorption maximum.              

EXAMPLE 2

12.0 g (0.02 mol) of Coupler (7) according to the present invention wasdissolved in 12.0 g of dibutyl phthalate as an organic solvent having ahigh boiling point and in 24 ml of ethyl acetate, and the resultingsolution was emulsified and dispersed in 200 g of a 10% by weightaqueous gelatin solution containing 1.5 g of sodiumdodecylbenzenesulfonate. An average particle size of the emulsifieddispersion was 0.12 μm.

The whole amount of the emulsified dispersion was added to 247 g ofsilver chlorobromide emulsion (silver content: 70 g per kg of emulsion,silver bromide content: 70 mol %), and the resulting mixture was coatedon a triacetate film support having a subbing layer in a silver coatingamount of 1.73 g/m². Onto the emulsion layer was coated a gelatin layerat a dry layer thickness of 1.0 μm to form a protective layer, wherebySample 2A-1 was prepared. As a gelatin hardener,1-oxy-3,5-dichloro-s-triazine sodium salt was used.

Samples 2A-2 to 2A-7 were prepared in the same manner as Sample 2A-1except for replacing the magenta coupler used in Sample 2A-1 with anequimolar amount of the magenta couplers according to the presentinvention shown in Table 2 below, respectively.

Further, Comparative Samples (2B-1), (2B-2) and (2B-3) were prepared inthe same manner as Sample 2A-1 except for replacing the magenta couplerused in Sample 2A-1 with an equimolar amount of Comparative Coupler(M-1) described above and Comparative Couplers (M-3) and (M-4) shownbelow, respectively. ##STR9##

Each sample thus-prepared was subjected to wedge exposure through athree color separation filter for sensitometry using a sensitometer (FWHtype, manufactured by Fuji Photo Film Co., Ltd.) equipped with a lightsource having a color temperature of 3,200° K. The amount of exposurewas 25 CMS and the exposure time was 0.1 second.

The exposed sample was processed in an automatic developing machineaccording to the processing steps shown below.

    ______________________________________                                        Processing Step                                                                            Temperature (°C.)                                                                    Time                                               ______________________________________                                        Color Development                                                                          37            3 min.   30 sec.                                   Bleach-Fixing                                                                              33            1 min.   30 sec.                                   Washing with Water                                                                         24 to 34      3 min.                                             Drying       70 to 80      1 min.                                             ______________________________________                                    

The composition of each processing solution which was used isillustrated below.

    ______________________________________                                        Color Developing Solution:                                                    Water                       800    ml                                         Diethylenetriaminepentaacetic acid                                                                        1.0    g                                          Nitrilotriacetic acid       2.0    g                                          Benzyl alcohol              15     ml                                         Diethylene glycol           10     ml                                         Sodium sulfite              2.0    g                                          Potassium bromide           1.0    g                                          Potassium carbonate         30     g                                          N-Ethyl-N-(β-methanesulfonamidoethyl)-                                                               4.5    g                                          3-methyl-4-aminoaniline sulfate                                               Hydroxylamine sulfate       3.0    g                                          Fluorescent brightening agent                                                                             1.0    g                                          (WHITEX 4B manufactured by                                                    Sumitomo Chemical Co., Ltd.)                                                  Water to make               1000   ml                                         pH (25° C.)          10.25                                             Bleach-Fixing Solution:                                                       Water                       400    ml                                         Ammonium thiosulfate        150    ml                                         (70% aqueous solution)                                                        Sodium sulfite              18     g                                          Ammonium iron(III) ethylendiamine-                                                                        55     g                                          tetraacetate                                                                  Disodium ethylenediamine-   5      g                                          tetraacetate                                                                  Water to make               1000   ml                                         pH (25° C)           6.70                                              ______________________________________                                    

Each of the samples thus processed was subjected to sensitometry. Theresults obtained are shown in Table 2 below.

                  TABLE 2                                                         ______________________________________                                                              Sensi-  Gra-   Maximum                                                        tivity  dation Density                                  Sample                                                                              Coupler         (s)*    (Υ)**                                                                        (Dm)                                     ______________________________________                                        2A-1   (7) (Present Invention)                                                                      85      2.70   2.80                                     2A-2   (2) (Present Invention)                                                                      90      2.80   2.85                                     2A-3   (3) (Present Invention)                                                                      92      2.82   2.86                                     2A-4  (13) (Present Invention)                                                                      88      2.75   2.82                                     2A-5  (28) (Present Invention)                                                                      89      2.78   2.83                                     2A-6  (34) (Present Invention)                                                                      80      2.60   2.75                                     2A-7  (38) (Present Invention)                                                                      80      2.81   2.90                                     2B-1  Comparative     100     2.50   2.65                                           Coupler (M-1)                                                           2B-2  Comparative     110     2.43   2.54                                           Coupler (M-3)                                                           2B-3  Comparative     112     2.47   2.53                                           Coupler (M-4)                                                           ______________________________________                                         *Sensitivity (s) is a value of the exposure amount necessary for providin     a density of fog plus 0.5 and shown relatively taking the value of            Comparative Sample (2B1) as 100.                                              **Gradation (Υ) means a slope of a sensitometric curve between a      point having a density of 0.5 and a point having a density of 2.5.       

From the results shown in Table 2, it can be seen that the magentacouplers according to the present invention exhibit high sensitivity andan excellent color forming property due to the reduced interaction withsilver in comparison with the comparative couplers.

EXAMPLE 3 Preparation of Sample 3A-1

A cellulose triacetate film support (thickness: 127 μm) having a subbinglayer was coated with each layer having the composition set forth belowto prepare a multilayer color photographic light-sensitive material.This photographic material was designated Sample 3A-1. Numerals indicateamounts added per m². It should be noted that the effects of thecompounds added are not limited to the uses described.

    ______________________________________                                        First Layer: Antihalation Layer                                               Black colloidal silver     0.25   g                                           Gelatin                    1.9    g                                           Ultraviolet light absorbing agent U-1                                                                    0.04   g                                           Ultraviolet light absorbing agent U-2                                                                    0.1    g                                           Ultraviolet light absorbing agent U-3                                                                    0.1    g                                           Ultraviolet light absorbing agent U-4                                                                    0.1    g                                           Ultraviolet light absorbing agent U-5                                                                    0.1    g                                           Ultraviolet light absorbing agent U-6                                                                    0.1    g                                           Organic solvent having a high boiling                                                                    0.1    g                                           point Oil-1                                                                   Second Layer: Intermediate Layer                                              Gelatin                    0.40   g                                           Compound Cpd-D             10     mg                                          Organic solvent having a high boiling                                                                    0.1    g                                           point Oil-3                                                                   Dye D-4                    0.4    mg                                          Third Layer: Intermediate Layer                                               Surface and internal fogged fine                                                                         0.05   g                                           grain silver iodobromide emulsion                                                                        (as silver)                                        (average grain size: 0.06 μm,                                              coefficient of variation:                                                     18%, AgI content: 1 mol %)                                                    Gelatin                    0.4    g                                           Fourth Layer:                                                                 Low-Speed Red-Sensitive Emulsion Layer                                        Emulsion A                 0.2    g                                                                    (as silver)                                          Emulsion B                 0.3    g                                                                    (as silver)                                          Gelatin                    0.8    g                                           Coupler C-1                0.15   g                                           Coupler C-2                0.05   g                                           Coupler C-7                0.05   g                                           Compound Cpd-D             10     mg                                          Organic solvent having a high boiling                                                                    0.1    g                                           point Oil-1                                                                   Fifth Layer:                                                                   Medium-Speed Red-Sensitive Emulsion Layer                                    Emulsion B                 0.2    g                                                                    (as silver)                                          Emulsion C                 0.3    g                                                                    (as silver)                                          Gelatin                    0.8    g                                           Coupler C-1                0.2    g                                           Coupler C-2                0.05   g                                           Coupler C-3                0.2    g                                           Organic solvent having a high boiling                                                                    0.1    g                                           point Oil-2                                                                   Sixth Layer:                                                                  High-Speed Red-Sensitive Emulsion Layer                                       Emulsion D                 0.4    g                                                                    (as silver)                                          Gelatin                    1.1    g                                           Coupler C-1                0.3    g                                           Coupler C-3                0.7    g                                           Additive P-1               0.1    g                                           Seventh Layer: Intermediate Layer                                             Gelatin                    0.6    g                                           Additive M3-1              0.3    g                                           Color mixing preventing agent Cpd-K                                                                      2.6    mg                                          Ultraviolet light absorbing agent U-1                                                                    0.1    g                                           Ultraviolet light absorbing agent U-6                                                                    0.1    g                                           Dye D-1                    0.02   g                                           Eighth Layer: Intermediate Layer                                              Surface and internal fogged silver                                                                       0.02   g                                           iodobromide emulsion (average grain                                                                      (as silver)                                        size: 0.06 μm, coefficient of                                              variation: 16%, AgI content: 0.3 mol %)                                       Gelatin                    1.0    g                                           Additive P-1               0.2    g                                           Color mixing preventing agent Cpd-J                                                                      0.1    g                                           Color mixing preventing agent Cpd-A                                                                      0.1    g                                           Ninth Layer:                                                                  Low-Speed Green-Sensitive Emulsion Layer                                      Emulsion E                 0.3    g                                                                    (as silver)                                          Emulsion F                 0.1    g                                                                    (as silver)                                          Emulsion G                 0.1    g                                                                    (as silver)                                          Gelatin                    0.5    g                                           Coupler (7) according to the                                                                             0.25   g                                           present invention                                                             Compound Cpd-B             0.03   g                                           Compound Cpd-D             10     mg                                          Compound Cpd-E             0.02   g                                           Compound Cpd-F             0.02   g                                           Compound Cpd-G             0.02   g                                           Compound Cpd-H             0.02   g                                           Organic solvent having a high boiling                                                                    0.1    g                                           point Oil-1                                                                   Organic solvent having a high boiling                                                                    0.1    g                                           point Oil-2                                                                   Tenth Layer:                                                                  Medium-Speed Green-Sensitive Emulsion Layer                                   Emulsion G                 0.3    g                                                                    (as silver)                                          Emulsion H                 0.1    g                                                                    (as silver)                                          Gelatin                    0.6    g                                           Coupler (7) according to the                                                                             0.3    g                                           present invention                                                             Compound Cpd-B             0.03   g                                           Compound Cpd-E             0.02   g                                           Compound Cpd-F             0.02   g                                           Compound Cpd-G             0.05   g                                           Compound Cpd-H             0.05   g                                           Organic solvent having a high boiling                                                                    0.01   g                                           point Oil-2                                                                   Eleventh Layer:                                                               High-Speed Green-Sensitive Emulsion Layer                                     Emulsion I                 0.5    g                                                                    (as silver)                                          Gelatin                    1.0    g                                           Coupler C-4                0.3    g                                           Coupler (7) according to the                                                                             0.1    g                                           present invention                                                             Compound Cpd-B             0.08   g                                           Compound Cpd-E             0.02   g                                           Compound Cpd-F             0.02   g                                           Compound Cpd-G             0.02   g                                           Compound Cpd-H             0.02   g                                           Organic solvent having a high boiling                                                                    0.02   g                                           point Oil-1                                                                   Organic solvent having a high boiling                                                                    0.02   g                                           point Oil-2                                                                   Twelfth Layer: Intermediate Layer                                             Gelatin                    0.6    g                                           Dye D-1                    0.1    g                                           Dye D-2                    0.05   g                                           Dye D-3                    0.07   g                                           Thirteenth Layer: Yellow Filter Layer                                         Yellow colloidal silver    0.1    g                                                                    (as silver)                                          Gelatin                    1.1    g                                           Color mixing preventing agent Cpd-A                                                                      0.01   g                                           Organic solvent having a high boiling                                                                    0.01   g                                           point Oil-1                                                                   Fourteenth Layer: Intermediate Layer                                          Gelatin                    0.6    g                                           Fifteenth Layer:                                                              Low-Speed Blue-Sensitive Emulsion Layer                                       Emulsion J                 0 4    g                                                                    (as silver)                                          Emulsion K                 0.1    g                                                                    (as silver)                                          Emulsion L                 0.1    g                                                                    (as silver)                                          Gelatin                    0.8    g                                           Coupler C-5                0.6    g                                           Sixteenth Layer:                                                              Medium-Speed Blue-Sensitive Emulsion Layer                                    Emulsion L                 0.1    g                                                                    (as silver)                                          Emulsion M                 0.4    g                                                                    (as silver)                                          Gelatin                    0.9    g                                           Coupler C-5                0.3    g                                           Coupler C-6                0.3    g                                           Seventeenth Layer:                                                            High-Speed Blue-Sensitive Emulsion Layer                                      Emulsion N                 0.4 g                                                                       (as silver)                                          Gelatin                    1.2    g                                           Coupler C-6                0.7    g                                           Eighteenth Layer: First Protective Layer                                      Gelatin                    0.7    g                                           Ultraviolet light absorbing agent U-1                                                                    0.04   g                                           Ultraviolet light absorbing agent U-2                                                                    0.01   g                                           Ultraviolet light absorbing agent U-3                                                                    0.03   g                                           Ultraviolet light absorbing agent U-4                                                                    0.03   g                                           Ultraviolet light absorbing agent U-5                                                                    0.05   g                                           Ultraviolet light absorbing agent U-6                                                                    0.05   g                                           Organic solvent having a high boiling                                                                    0.02   g                                           point Oil-1                                                                   Formalin scavenger Cpd-C   0.2    g                                           Formalin scavenger Cpd-I   0.4    g                                           Dye D-3                    0.05   g                                           Nineteenth Layer: Second Protective Layer                                     Colloidal silver           0.1    g                                                                    (as silver)                                          Fine grain silver iodobromide                                                                            0.1    g                                           emulsion (average grain size:                                                                            (as silver)                                        0.6 μm, AgI content: 1 mol %)                                              Gelatin                    0.4    g                                           Twentieth Layer: Third Protective Layer                                       Gelatin                    0.4    g                                           Polymethyl methacrylate (average                                                                         0.1    g                                           particle size: 1.5 μm)                                                     Methyl methacrylate-acrylic acid                                                                         0.1    g                                           (4:6) copolymer (average particle                                             size: 1.5 μm)                                                              Silicone oil               0.03   g                                           Surfactant W-1             3.0    mg                                          Surfactant W-2             0.03   g                                           ______________________________________                                    

In addition to the above-described components, Additives F-1 to F-8 wereadded to each of the emulsion layers. Further, Gelatin hardener H-1 andSurfactants W-3 and W-4 for coating and emulsification were added toeach layer. Moreover, phenol, 1,2-benzisothiazolin-3-one,2-phenoxyethanol and phenethyl alcohol were added to each layer asantiseptics and antimolds.

The silver iodobromide emulsions used for the preparation of Sample 3A-1were as follows.

    __________________________________________________________________________                                  Average Grain                                                                         Coefficient of                                                                       AgI Content                      Emulsion                                                                           Type of Grain            Size (μm)                                                                          Variation (%)                                                                        (%)                              __________________________________________________________________________    A    Monodispersed tetradecahedral grain                                                                    0.25    16     3.7                              B    Monodispersed cubic internal latent image type grain                                                   0.30    10     3.3                              C    Monodispersed tetradecahedral grain                                                                    0.30    18     5.0                              D    Monodispersed twin grain 0.60    25     2.0                              E    Monodispersed cubic grain                                                                              0.17    17     4.0                              F    Monodispersed cubic grain                                                                              0.20    16     4.0                              G    Monodispersed cubic internal latent image type grain                                                   0.25    11     3.5                              H    Monodispersed cubic internal latent image type grain                                                   0.30     9     3.5                              I    Monodispersed tabular grain                                                                            0.80    28     1.5                                   (average aspect ratio: 4.0)                                              J    Monodispersed tetradecahedral grain                                                                    0.30    18     4.0                              K    Monodispersed tetradecahedral grain                                                                    0.37    17     4.0                              L    Monodispersed cubic internal latent image type grain                                                   0.46    14     3.5                              M    Monodispersed cubic grain                                                                              0.55    13     4.0                              N    Monodispersed tabular grain                                                                            1.00    33     1.3                                   (average aspect ratio: 7.0)                                              __________________________________________________________________________    Spectral sensitization methods for Emulsions A to N were as follows.                            Amount of                                                                     Sensitizing Dye                                             Emulsion                                                                             Sensitizing Dye                                                                          (g/mol AgX)                                                                              Period of Addition of Sensitizing                __________________________________________________________________________                                 Dye                                              A      S-1        0.025      Just after chemical sensitization                       S-2        0.25       Just after chemical sensitization                B      S-1        0.01       Just after end of grain formation                       S-2        0.25       Just after end of grain formation                C      S-1        0.02       Just after chemical sensitization                       S-2        0.25       Just after chemical sensitization                D      S-1        0.01       Just after chemical sensitization                       S-2        0.10       Just after chemical sensitization                       S-7        0.01       Just after chemical sensitization                E      S-3        0.5        Just after chemical sensitization                       S-4        0.1        Just after chemical sensitization                F      S-3        0.3        Just after chemical sensitization                       S-4        0.1        Just after chemical sensitization                G      S-3        0.25       Just after end of grain formation                       S-4        0.08       Just after end of grain formation                H      S-3        0.2        During grain formation                                  S-4        0.06       During grain formation                           I      S-3        0.3        Just before start of chemical sensitization             S-4        0.07       Just before start of chemical sensitization             S-8        0.1        Just before start of chemical sensitization      J      S-6        0.2        During grain formation                                  S-5        0.05       During grain formation                           K      S-6        0.2        During grain formation                                  S-5        0.05       During grain formation                           L      S-6        0.22       Just after end of grain formation                       S-5        0.06       Just after end of grain formation                M      S-6        0.15       Just after chemical sensitization                       S-5        0.04       Just after chemical sensitization                N      S-6        0.22       Just after end of grain formation                       S-5        0.06       Just after end of grain formation                __________________________________________________________________________

Chemical formulas or names of the compounds used in Sample 3A-1 areillustrated below. ##STR10##

Samples (3A-2) to (3A-7) were prepared in the same manner as describedfor Sample (3A-1) except that Coupler (7) according to the presentinvention used in Sample (3A-1) was replaced with an equimolar amount ofCouplers (4), (10), (17), (20) and (25) according to the presentinvention, respectively.

Further, Comparative Samples (3B-1) to (3B-3) were prepared in the samemanner as described for Sample (3A-1) except that Coupler (7) accordingto the present invention used in Sample (3A-1) was replaced with anequimolar amount of Comparative Couplers (M-3) and (M-4) described aboveand Comparative Coupler (M-5) shown below, respectively. ##STR11##

These samples thus-prepared were subjected to exposure for sensitometryand then processed by an automatic developing machine according to theprocessing steps shown below.

    ______________________________________                                        Processing Step                                                                              Time     Temperature (°C.)                              ______________________________________                                        First Development                                                                            6 minutes                                                                              38                                                    Washing with Water                                                                           2 minutes                                                                              38                                                    Reversal       2 minutes                                                                              38                                                    Color Development                                                                            6 minutes                                                                              38                                                    Controlling    2 minutes                                                                              38                                                    Bleaching      6 minutes                                                                              38                                                    Fixing         4 minutes                                                                              38                                                    Washing with Water                                                                           4 minutes                                                                              38                                                    Stabilizing    1 minute room temperature                                      ______________________________________                                    

Drying

The composition of each processing solution which was used isillustrated below.

    ______________________________________                                        First Developing Solution:                                                    Water                      700    ml                                          Pentasodium nitrilo-N,N,N- 2      g                                           trimethylenephosphonate                                                       Sodium sulfite             20     g                                           Hydroquinonemonosulfonate  30     g                                           Sodium carbonate (monohydrate)                                                                           30     g                                           1-Phenyl-4-methyl-4-hydroxy-                                                                             2      g                                           methyl-3-pyrazolidone                                                         Potassium bromide          2.5    g                                           Potassium thiocyanate      1.2    g                                           Potassium iodide (0.1% soln.)                                                                            2      ml                                          Water to make              100    ml                                          Reversal Solution:                                                            Water                      400    ml                                          Pentasodium nitrilo-N,N,N-tri-                                                                           3      g                                           methylenephosphonate                                                          Stannous chloride (dihydrate)                                                                            1      g                                           p-Aminophenol              0.1    g                                           Sodium hydroxide           8      g                                           Glacial acetic acid        15     ml                                          Water to make              1000   ml                                          Color Developing Solution:                                                    Water                      700    ml                                          Pentasodium nitrilo-N,N,N-tri-                                                                           3      g                                           methylenephosphonate                                                          Sodium sulfite             7      g                                           Sodium tertiary phosphate (12 hydrate)                                                                   36     g                                           Potassium bromide          1      g                                           Potassium iodide (0.1% soln.)                                                                            90     ml                                          Sodium hydroxide           3      g                                           Citrazinic acid            1.5    g                                           N-Ethyl-N-(β-methanesulfonamidoethyl)-                                                              11     g                                           3-methyl-4-aminoaniline sulfate                                               3,6-Dithiaoctane-1,8-diol  1      g                                           Water to make              1000   ml                                          Controlling Solution:                                                         Water                      700    ml                                          Sodium sulfite             12     g                                           Sodium ethylenediaminetetraacetate                                                                       8      g                                           (dihydrate)                                                                   Thioglycerol               0.4    ml                                          Glacial acetic acid        3      ml                                          Water to make              1000   ml                                          Bleaching Solution:                                                           Water                      800    ml                                          Sodium ethylenediaminetetraacetate                                                                       2      g                                           (dihydrate)                                                                   Ammonium iron(III) ethylenediamine-                                                                      120    g                                           tetraacetate (dihydrate)                                                      Potassium bromide          100    g                                           Water to make              1000   ml                                          Fixing Solution:                                                              Water                      800    ml                                          Sodium thiosulfate         80.0   g                                           Sodium sulfite             5.0    g                                           Sodium bisulfite           5.0    g                                           Water to make              1000   ml                                          Stabilizing Solution:                                                         Water                      800    ml                                          Formalin (37 wt %)         5.0    g                                           Fuji Drywel (surface active agent,                                                                       5.0    g                                           manufactured by Fuji Photo Film                                               Co., Ltd.)                                                                    Water to make              1000   ml                                          ______________________________________                                    

Each of the samples thus processed was subjected to sensitometry. Theresults obtained are shown in Table 3 below.

                  TABLE 3                                                         ______________________________________                                                              Gradation Maximum Density                               Sample                                                                              Coupler         (Υ)*                                                                            (Dm)                                          ______________________________________                                        3A-1   (7) (Present Invention)                                                                      2.65      2.70                                          3A-2   (4) (Present Invention)                                                                      2.70      2.80                                          3A-3  (10) (Present Invention)                                                                      2.75      2.90                                          3A-4  (17) (Present Invention)                                                                      2.68      2.79                                          3A-5  (20) (Present Invention)                                                                      2.66      2.71                                          3A-6  (25) (Present Invention)                                                                      2.69      2.82                                          3B-1  Comparative     2.48      2.66                                                Coupler (M-3)                                                           3B-2  Comparative     2.40      2.53                                                Coupler (M-4)                                                           3B-3  Comparative     2.46      2.52                                                Coupler (M-5)                                                           ______________________________________                                         *Gradation (Υ) means a slope of a sensitometric curve between a       point having a density of 0.5 and a point having a density of 2.5.       

From the results shown in Table 3, it can be seen that the magentacouplers according to the present invention exhibit excellent colorforming property due to the reduced interaction with silver incomparison with the comparative couplers.

EXAMPLE 4

A paper support, both surfaces of which were laminated withpolyethylene, was subjected to corona discharge treatment and providedwith a gelatin subbing layer containing sodium dodecylbenzenesulfonate,and then coated with the photographic constituting layers as shown belowto prepare a multilayer color printing paper, which is denoted as Sample(4A-1). The coating solutions were prepared in the following manner.

Preparation of Coating Solution for First Layer

19. 1 g of Yellow coupler (ExY) , 4. 4 g of Color image stabilizer(Cpd-1) and 0.7 g of Color image stabilizer (Cpd-7) were dissolved in27.2 ml of ethyl acetate, 4.1 g of Solvent (Solv-3) and 4.1 g of Solvent(Solv-7), and the resulting solution was emulsified and dispersed in 185ml of a 10% aqueous gelatin solution containing 8 ml of a 10% aqueoussolution of sodium dodecylbenzenesulfonate to prepare EmulsifiedDispersion A. Separately, Silver Chlorobromide Emulsion A (cubic grains;a mixture of large grain size emulsion (average grain size of 0.88 μm)and a small grain size emulsion (average grain size of 0.70 μm) in 3:7by molar ratio of silver; coefficient of variation of grain size: 0.08and 0.10, respectively; 0.3 mol % silver bromide based on the whole ofgrains being localized at a part of the surface of grains respectively)was prepared. Blue-Sensitive Sensitizing Dyes A and B shown below wereeach added to the emulsion in an amount of 2.0×10⁻⁴ mol per mol ofsilver in the case of the large grain size emulsion and in an amount of2.5×10⁻⁴ mol per mol of silver in the case of the small grain sizeemulsion. The emulsion was chemically ripened by adding a sulfursensitizer and a gold sensitizer. Emulsified Dispersion A describedabove was mixed with Silver Chlorobromide Emulsion A, with theconcentration of the resulting mixture being controlled to form thecomposition shown below, whereby the coating solution for the firstlayer was prepared.

Coating solutions for the second layer to the seventh layer wereprepared in a similar manner as described for the coating solution forthe first layer.

1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardenerin each layer.

Further, Cpd-10 and Cpd-11 were added to each layer in total amounts of25.0 mg/m² and 50.0 mg/m² respectively.

The following spectral sensitizing dyes were added to the silverchlorobromide emulsions in the light-sensitive emulsion layersrespectively. ##STR12## (Amount added: 2.0×10⁻⁴ mol per mol of silverhalide of each were added in the large grain size emulsion and 2.5×10⁻⁴mol per mol of silver halide of each were added in the small grain sizeemulsion) ##STR13## (Amount added: 4.0×10⁻⁴ mol per mol of silver halidein the large grain size emulsion and 5.6×10⁻⁴ mol per mol of silverhalide in the small grain size emulsion) and ##STR14## (Amount added:7.0×10⁻⁵ mol per mol of silver halide in the large grain size emulsionand 1.0×10⁻⁵ mol per mol of silver halide in the small grain sizeemulsion) ##STR15## (Amount added: 0.9×10⁻⁴ mol per mol of silver halidein the large grain size emulsion and 1.1×10⁻⁴ mol per mol of silverhalide in the small grain size emulsion)

To the red-sensitive emulsion layer was added the compound shown belowin an amount of 2.6×10⁻³ mol per mol of silver halide. ##STR16##

To the blue-sensitive emulsion layer, green-sensitive emulsion layer andred-sensitive emulsion layer were added1-(5-methylureidophenyl)-5-mercapto-tetrazole in amounts of 8.5×10⁻⁵mol, 7.7×10⁻⁴ mol and 2.5×10⁻⁴ mol per mol of silver halide,respectively.

Further, to the blue-sensitive emulsion layer and green-sensitiveemulsion layer were added 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene inamounts of 1×10⁻⁴ mol and 2×10⁻⁴ mol per mol of silver halide,respectively.

Moreover, in order to prevent irradiation, the following dyes were addedto the emulsion layers. The coating amounts thereof are shown inparentheses. ##STR17##

Layer Construction

The composition of each layer is shown below. The numerical valuesdenote the coating amounts of components in the unit of g/m². Thecoating amount of silver halide emulsion is indicated in terms of thesilver coating amount.

    ______________________________________                                        Support   Polyethylene laminated paper (the poly-                                       ethylene coating containing a white                                           pigment (TiO.sub.2) and a bluish dye (ultra-                                  marine) on the first layer side)                                    First Layer                                                                             Silver Chlorobromide Emulsion                                                                         0.30                                        (Blue-sensitive                                                                         A described above                                                   layer)    Gelatin                 1.86                                                  Yellow coupler (ExY)    0.82                                                  Color image stabilizer (Cpd-1)                                                                        0.19                                                  Solvent (Solv-3)        0.18                                                  Solvent (Solv-7)        0.18                                                  Color image stabilizer (Cpd-7)                                                                        0.06                                        Second Layer                                                                            Gelatin                 0.99                                        (Color mixing                                                                           Color mixing preventing agent                                                                         0.08                                        preventing                                                                              (Cpd-5)                                                             layer)    Solvent (Solv-1)        0.16                                                  Solvent (Solv-4)        0.08                                        Third Layer                                                                             Silver chlorobromide emulsion                                                                         0.12                                        (Green-   (cubic grains, mixture of large                                     sensitive grain size emulsion (average                                        layer)    grain size of 0.55 μm) and small                                           grain size emulsion (average grain                                            size of 0.39 μm) in 1:3 by molar                                           ratio of silver, coefficient of                                               variation of grain size: 0.10 and                                             0.08, respectively, 0.8 mol % silver                                          bromide based on the whole of                                                 grains being localized at a part                                              of the surface of grains                                                      respectively)                                                                 Gelatin                 1.24                                                  Coupler (7) acording to the                                                                           0.23                                                  present invention                                                             Color image stabilizer (Cpd-2)                                                                        0.03                                                  Color image stabilizer (Cpd-3)                                                                        0.16                                                  Color image stabilizer (Cpd-4)                                                                        0.02                                                  Color image stabilizer (Cpd-9)                                                                        0.02                                                  Solvent (Solv-2)        0.40                                        Fourth Layer                                                                            Gelatin                 1.58                                        (Ultraviolet                                                                            Ultraviolet light absorbing                                                                           0.47                                        light absorb-                                                                           agent (UV-1)                                                        ing layer)                                                                              Color mixing preventing agent                                                                         0.05                                                  (Cpd-5)                                                                       Solvent (Solv-5)        0.24                                        Fifth Layer                                                                             Silver chlorobromide emulsion                                                                         0.23                                        (Red-sensitive                                                                          (cubic grains, mixture of large                                     layer)    grain size emulsion (average                                                  grain size of 0.58 μm) and small                                           grain size emulsion (average                                                  grain size of 0.45 μm) in 1:4                                              by molar ratio of silver,                                                     coefficient of variation of                                                   grain size: 0.09 and 0.11,                                                    respectively, 0.6 mol % silver                                                bromide based on the whole of                                                 grains being localized at a                                                   part of the surface of grains                                                 respectively)                                                                 Gelatin                 1.34                                                  Cyan coupler (ExC)      0.32                                                  Color image stabilizer (Cpd-2)                                                                        0.03                                                  Color image stabilizer (Cpd-4)                                                                        0.02                                                  Color image stabilizer (Cpd-6)                                                                        0.18                                                  Color image stabilizer (Cpd-7)                                                                        0.40                                                  Color image stabilizer (Cpd-8)                                                                        0.05                                                  Solvent (Solv-6)        0.14                                        Sixth Layer                                                                             Gelatin                 0.53                                        (Ultraviolet                                                                            Ultraviolet light absorbing                                                                           0.16                                        light absorb-                                                                           agent (UV-1)                                                        ing layer)                                                                              Color mixing preventing agent                                                                         0.02                                                  (Cpd-5)                                                                       Solvent (Solv-5)        0.08                                        Seventh Layer                                                                           Gelatin                 1.33                                        (Protective                                                                             Acryl-modified polyvinyl                                                                              0.17                                        layer)    alcohol copolymer (Degree                                                     of modification: 17%)                                                         Liquid paraffin         0.03                                        ______________________________________                                    

Chemical formulas or names of the compounds used in Sample 4A-1 areillustrated below. ##STR18##

Samples (4A-2) to (4A-7) were prepared in the same manner as describedfor Sample (4A-1) except that Coupler (7) according to the presentinvention used in Sample (4A-1) was replaced with an equimolar amount ofCouplers (9), (11), (15), (19), (33) and (40) according to the presentinvention, respectively.

Further, comparative Samples (4B-1) to (4B-3) were prepared in the samemanner as described for Sample (4A-1) except that Coupler (7) accordingto the present invention used in Sample (4A-1) was replaced with anequimolar amount of Comparative Couplers (M-1), (M-3) and (M-4)described above, respectively.

Each sample thus-prepared was subjected to wedge exposure through athree color separating filter for sensitometry using a sensitometer (FWEtype, manufactured by Fuji Photo Film Co., Ltd.) equipped with a lightsource having a color temperature of 3,200° K. The amount of exposurewas 250 CMS and the exposure time was 0.1 second.

The exposed sample was subjected to a continuous processing (runningtest) by a paper processor according to the processing steps describedbelow until the amount of replenishment of color development reached thetwice volume of the tank capacity of color development.

    ______________________________________                                                                    Amount of*                                                                              Tank                                    Processing                                                                             Temperature        Replenishment                                                                           capacity                                Step     (°C.)                                                                             Time    (ml)      (l)                                     ______________________________________                                        Color    35         45 sec. 161       17                                      Development                                                                   Bleach-Fixing                                                                          30-35      45 sec. 215       17                                      Rinse (1)                                                                              30-35      20 sec. --        10                                      Rinse (2)                                                                              30-35      20 sec. --        10                                      Rinse (3)                                                                              30-35      20 sec. 350       10                                      Drying   70-80      60 sec.                                                   ______________________________________                                         *The amount of replenishment is per m.sup.2 of photographic lightsensitiv     material                                                                 

The rinse steps were conducted using a three-tank countercurrent systemfrom Rinse (3) to Rinse (1).

The composition of each processing solution used is illustrated below.

    ______________________________________                                                             Tank   Re-                                                                    Solution                                                                             plenisher                                         ______________________________________                                        Color Developing Solution:                                                    Water                  800    ml    800  ml                                   Ethylenediamine-N,N,N,N-                                                                             1.5    g     2.0  g                                    tetramethylenephosphonic acid                                                 Potassium bromide      0.015  g     --                                        Triethanolamine        8.0    g     12.0 g                                    Sodium chloride        1.4    g     --                                        Potassium carbonate    25     g     25   g                                    N-Ethyl-N-(β-methanesulfon-                                                                     5.0    g     7.0  g                                    amidoethyl)-3-methyl-4-amino-                                                 aniline sulfate                                                               N,N-Bis(carboxymethyl)hydrazine                                                                      4.0    g     5.0  g                                    N,N-Di(sulfoethyl)hydroxylamine                                                                      4.0    g     5.0  g                                    monosodium salt                                                               Fluorescent brightening agent                                                                        1.0    g     2.0  g                                    (WHITEX 4B manufactured by                                                    Sumitomo Chemical Co., Ltd.)                                                  Water to make          1000   ml    1000 ml                                   pH (at 25° C.)  10.05        10.45                                     Bleach-Fixing Solution:                                                       (both tank solution and replenisher)                                          Water                     400    ml                                           Ammonium thiosulfate (70%)                                                                              100    ml                                           Sodium sulfite            17     g                                            Ammonium Iron(III) ethylenediamine-                                                                     55     g                                            tetraacetate                                                                  Disodium ethylenediaminetetraacetate                                                                    5      g                                            Ammonium bromide          40     g                                            Water to make             1000   ml                                           pH (at 25° C.)     6.0                                                 ______________________________________                                    

Rinse Solution: (both tank solution and replenisher)

Ion-exchanged water (calcium and magnesium contents: not more than 3 ppmrespectively)

Each of the samples thus processed was subjected to sensitometry. Theresults obtained are shown in Table 4 below.

                  TABLE 4                                                         ______________________________________                                                                       Gra-  Maximum                                                       Sensitivity                                                                             dation                                                                              Density                                  Sample                                                                              Coupler        (s)*      (Υ)**                                                                       (Dm)                                     ______________________________________                                        4A-1   (7)           90        2.74  2.85                                           (Present Invention)                                                     4A-2  (9)            93        2.70  2.80                                           (Present Invention)                                                     4A-3  (11)           91        2.73  2.82                                           (Present Invention)                                                     4A-4  (15)           90        2.75  2.85                                           (Present Invention)                                                     4A-5  (19)           85        2.80  2.90                                           (Present Invention)                                                     4A-6  (33)           87        2.78  2.88                                           (Present Invention)                                                     4A-7  (40)           85        2.82  2.92                                           (Present Invention)                                                     4B-1  Comparative    100       2.57  2.62                                           Coupler (M-1)                                                           4B-2  Comparative    110       2.42  2.50                                           Coupler (M-3)                                                           4B-3  Comparative    113       2.45  2.49                                           Coupler (M-4)                                                           ______________________________________                                         *Sensitivity (s) is a value of the exposure amount necessary for providin     a density of fog plus 0.5 and shown relatively taking the value of            Comparative Sample (4B1) as 100.                                              **Gradation (Υ) means a slope of a sensitometric curve between a      point having a density of 0.5 and a point having a density of 2.5.       

From the results shown in Table 4, it can be seen that the magentacouplers according to the present invention exhibit high sensitivity andexcellent color forming property due to the reduced interaction withsilver in comparison with the comparative couplers.

EXAMPLE 5

On a cellulose triacetate film support provided with a subbing layer wascoated each layer having the composition set forth below to prepare amultilayer color photographic light-sensitive material which wasdesignated Sample 5A-1.

With respect to the compositions of the layers, the coating amounts ofsilver halide and colloidal silver are shown by g/m² units in terms ofsilver, the coating amounts of couplers, additives and gelatin are shownby g/m² units, and the coating amounts of sensitizing dyes are shown bymol number per mol of silver halide present in the same layer.

    ______________________________________                                        First Layer: Antihalation Layer                                               Black colloidal silver     0.15                                               Gelatin                    1.90                                               ExM-8                      2.0 × 10.sup.-2                              Second Layer: Intermediate Layer                                              Gelatin                    2.10                                               UV-1                       3.0 × 10.sup.-2                              UV-2                       6.0 × 10.sup.-2                              UV-3                       7.0 × 10.sup.-2                              ExF-1                      4.0 × 10.sup.-3                              Solv 5-2                   7.0 × 10.sup.-2                              Third Layer:                                                                  Low-Speed Red-Sensitive Emulsion Layer                                        Silver iodobromide emulsion                                                                              0.50                                               (AgI: 2 mol %, internal high AgI                                                                         (as silver)                                        type, diameter corresponding to                                               sphere: 0.3 μm, coefficient of                                             variation of diameter corresponding                                           to sphere: 29%, mixture of regular                                            and twin grains, diameter/thickness ratio: 2.5)                               Gelatin                    1.50                                               ExS-1                      1.0 × 10.sup.-4                              ExS-2                      3.0 × 10.sup.-4                              ExS-3                      1.0 × 10.sup.-5                              ExC-3                      0.22                                               ExC-4                      3.0 × 10.sup.-2                              Solv 5-1                   7.0 × 10.sup.-3                              Fourth Layer:                                                                 Medium-Speed Red-Sensitive Emulsion Layer                                     Silver iodobromide emulsion                                                                              0.85                                               (AgI: 4 mol %, internal high                                                                             (as silver)                                        AgI type, diameter corresponding                                              to sphere: 0.55 μm, coefficient of                                         variation of diameter corresponding                                           to sphere: 20%, mixture of regular                                            and twin grains, diameter/thickness ratio: 1.0)                               Gelatin                    2.00                                               ExS-1                      1.0 × 10.sup.-4                              ExS-2                      3.0 × 10.sup.-4                              ExS-3                      1.0 × 10.sup.-5                              ExC-2                      8.0 × 10.sup.-2                              ExC-3                      0.33                                               ExY-13                     2.0 × 10.sup.-2                              ExY-14                     1.0 × 10.sup.-2                              Cpd 5-10                   1.0 × 10.sup.-4                              Solv 5-1                   0.10                                               Fifth Layer:                                                                  High-Speed Red-sensitive Emulsion Layer                                       Silver iodobromide emulsion                                                                              0.70                                               (AgI: 10 mol %, internal high                                                                            (as silver)                                        AgI type, diameter corresponding                                              to sphere: 0.7 μm, coefficient                                             of variation of diameter corre-                                               sponding to sphere: 30%, mixture                                              of regular and twin grains,                                                   diameter/thickness ratio: 2.0)                                                Gelatin                    1.60                                               ExS-1                      1.0 × 10.sup.-4                              ExS-2                      3.0 × 10.sup.-4                              ExS-3                      1.0 × 10.sup.-5                              ExC-5                      7.0 × 10.sup.-2                              ExC-6                      8.0 × 10.sup.-2                              Solv 5-1                   0.15                                               Solv 5-2                   8.0 × 10.sup.-2                              Sixth Layer: Intermediate Layer                                               Gelatin                    1.10                                               P-2                        0.17                                               Cpd 5-1                    0.10                                               Cpd 5-4                    0.17                                               Solv 5-1                   5.0 ×  10.sup.-2                             Seventh Layer:                                                                Low-Speed Green-Sensitive Emulsion Layer                                      Silver iodobromide emulsion                                                                              0.30                                               (AgI: 2 mol %, internal high                                                                             (as silver)                                        AgI type, diameter corresponding                                              to sphere: 0.3 μm, coefficient                                             of variation of diameter corre-                                               sponding to sphere: 28%, mixture                                              of regular and twin grains,                                                   diameter/thickness ratio: 2.5)                                                Gelatin                    0.50                                               ExS-4                      5.0 × 10.sup.-4                              ExS-5                      2.0 × 10.sup.-4                              ExS-6                      0.3 × 10.sup.-4                              ExM-8                      3.0 × 10.sup.-2                              Coupler (7) according to the                                                                             0.20                                               present invention                                                             ExY-13                     3.0 × 10.sup.-2                              Cpd-11                     7.0 × 10.sup.-3                              Solv-1                     0.20                                               Eighth Layer:                                                                 Medium-Speed Green-Sensitive Emulsion Layer                                   Silver iodobromide emulsion                                                                              0.70                                               (AgI: 4 mol %, internal high                                                                             (as silver)                                        AgI type, diameter corresponding                                              to sphere: 0.55 μm, coefficient                                            of variation of diameter corre-                                               sponding to sphere: 20%, mixture                                              of regular and twin grains,                                                   diameter/thickness ratio: 4.0)                                                Gelatin                    1.00                                               ExS-4                      5.0 × 10.sup.-4                              ExS-5                      2.0 × 10.sup.-4                              ExS-6                      3.0 × 10.sup.-5                              ExM-8                      3.0 × 10.sup.-2                              Coupler (7) according to the present invention                                                           0.25                                               ExM-10                     1.5 × 10.sup.-2                              ExY-13                     4.0 ×  10.sup.-2                             Cpd 5-11                   9.0 × 10.sup.-3                              Solv 5-1                   0.20                                               Ninth Layer:                                                                  High-Speed Green-Sensitive Emulsion Layer                                     Silver iodobromide emulsion                                                                              0.50                                               (AgI: 10 mol %, internal high                                                                            (as silver)                                        AgI type, diameter corresponding                                              to sphere: 0.7 μm, coefficient of                                          variation of diameter corresponding                                           to sphere: 30%, mixture of regular                                            and twin grains, diameter/thickness ratio: 2.0)                               Gelatin                    0.90                                               ExS-4                      2.0 × 10.sup.-4                              ExS-5                      2.0 × 10.sup.-4                              ExS-6                      2.0 × 10.sup.-5                              ExS-7                      3.0 × 10.sup.-4                              ExM-8                      2.0 × 10.sup.-2                              Coupler (7) according to the present invention                                                           8.0 × 10.sup.-2                              Cpd 5-2                    1.0 × 10.sup.-2                              Cpd 5-9                    2.0 × 10.sup.-4                              Cpd 5-10                   2.0 × 10.sup.-4                              Solv 5-1                   0.20                                               Solv 5-2                   5.0 × 10.sup.-2                              Tenth Layer: Yellow Filter Layer                                              Gelatin                    0.90                                               Yellow colloidal silver    5.0 × 10.sup.-2                              Cpd 5-1                    0.20                                               Solv 5 1                   0.15                                               Eleventh Layer:                                                               Low-Speed Blue-sensitive Emulsion Layer                                       Silver iodobromide emulsion                                                                              0.40                                               (AgI: 4 mol %, internal high                                                                             (as silver)                                        AgI type, diameter corresponding                                              to sphere: 0.5 μm, coefficient                                             of variation of diameter corre-                                               sponding to sphere: 15%, octahedral grains)                                   Gelatin                    1.00                                               ExS-8                      2.0 × 10.sup.-2                              ExY-13                     9.0 × 10.sup.-2                              ExY-15                     0.90                                               Cod 5-2                    1.0 × 10.sup.-2                              Solv 5-1                   0.30                                               Twelfth Layer:                                                                High-Speed Blue-sensitive Emulsion Layer                                      Silver iodobromide emulsion                                                                              0.50                                               (AgI: 10 mol %, internal high                                                                            (as silver)                                        AgI type, diameter corresponding                                              to sphere: 1.3 μm, coefficient of                                          variation of diameter corresponding                                           to sphere: 25%, mixture of regular                                            and twin grains, diameter/thickness ratio: 4.5)                               Gelatin                    0.60                                               ExS-8                      1.0 × 10.sup.-4                              ExY-15                     0.12                                               Cod 5-2                    1.0 × 10.sup.-3                              Solv 5-1                   4.0 × 10.sup.-2                              Thirteenth Layer: First Protective Layer                                      Fine grain silver iodobromide                                                                            0.20                                               (AgI: 1 mol %, average grain size: 0.07 μm)                                Gelatin                    0.80                                               UV-2                       0.10                                               UV-3                       0.10                                               UV-4                       0.20                                               Solv 5-3                   4.0 × 10.sup.-2                              P5-2                       9.0 × 10.sup.-2                              Fourteenth Layer: Second Protective Layer                                     Gelatin                    0.90                                               B-1 (diameter: 1.5 μm)  0.10                                               B-2 (diameter: 1.5 μm)  0.10                                               B-3                        2.0 × 10.sup.-2                              H-1                        0.40                                               ______________________________________                                    

Further, Cpd 5-3, Cpd 5-5, Cpd 5-6, Cpd 5-7, Cpd 5-8, P5-1, W5-1, W5-2and W5-3 were added in order to improve preservability, processingproperty, pressure resistibility, antimold and antibacterial action,antistatic property and coating property.

Moreover, n-butyl-p-hydroxybenzoate was added. In addition, B-4, F5-1,F5-4, F5-5, F5-6, F5-7, F5-8, F5-9, F5-10, F5-11, F5-13, iron salt, leadsalt, gold salt, platinum salt, iridium salt and sodium salt wereincorporated.

Chemical formulas or the names of the compounds used in Sample 5A-1 areillustrated below. ##STR19##

Samples (5A-2) to (5A-7) were prepared in the same manner as describedfor Sample (5A-1) except that Coupler (7) according to the presentinvention used in Sample (5A-1) was replaced with an equimolar amount ofCouplers (12), (24), (27), (31), (36) and (41) according to the presentinvention, respectively.

Further, Comparative Samples (5B-1) to (5B-3) were prepared in the samemanner as described for Sample (5A-1) except that Coupler (7) accordingto the present invention used in Sample (5A-1) was replaced with anequimolar amount of Comparative Couplers (M-3), (M-4) and (M-5) used inExample 3 above, respectively.

These samples thus-prepared were subjected to exposure for sensitometryand then processed in an automatic developing machine according to theprocessing steps shown below.

    ______________________________________                                                      Processing  Processing                                          Processing Step                                                                             Time        Temperature (°C.)                            ______________________________________                                        Color Development                                                                           3 min.  15 sec. 38                                              Bleaching     1 min.  00 sec. 38                                              Bleach-Fixing 3 min.  15 sec. 38                                              Washing with Water (1)                                                                              15 sec. 35                                              Washing with Water (2)                                                                      1 min.  00 sec. 35                                              Stabilizing           40 sec. 38                                              Drying        1 min.  15 sec. 55                                              ______________________________________                                    

The composition of each processing solution used is illustrated below.

    ______________________________________                                        Color Developing Solution:                                                    Diethylenetriaminepentaacetic acid                                                                      1.0    g                                            1-Hydroxyethylidene-1,1-diphosphonic                                                                    3.0    g                                            acid                                                                          Sodium sulfite            4.0    g                                            Potassium carbonate       30.0   g                                            Potassium bromide         1.4    g                                            Potassium iodide          1.5    mg                                           Hydroxylamine sulfate     2.4    g                                            4-(N-Ethyl-N-β-hydroxyethylamino)-                                                                 4.5    g                                            2-methylaniline sulfate                                                       Water to make             1000   ml                                           pH                        10.05                                               Bleaching Solution:                                                           Ammonium iron(III) ethylenediamine-                                                                     120.0  g                                            tetraacetate dihydrate                                                        Disodium ethylenediaminetetraacetate                                                                    10.0   g                                            Ammonium bromide          100.0  g                                            Ammonium nitrate          10.0   g                                            Bleach accelerating agent 0.005  mol                                           ##STR20##                                                                    Aqueous ammonia (27%)     15.0   ml                                           Water to make             1000   ml                                           pH                        6.3                                                 Bleach-Fixing Solution:                                                       Ammonium iron(III) ethylenediamine-                                                                     50.0   g                                            tetraacetate dihydrate                                                        Disodium ethylenediaminetetraacetate                                                                    5.0    g                                            Sodium sulfite            12.0   g                                            Aqueous solution of ammonium                                                                            240.0  ml                                           thiosulfate (70%)                                                             Aqueous ammonia (27%)     6.0    ml                                           Water to make             1000   ml                                           pH                                                                            ______________________________________                                    

Washing Water

City water was passed through a mixed bed type column filled with anH-type strong acidic cation exchange resin (amberlite IR-120Bmanufactured by Rhom & Haas Co.) and an OH-type anion exchange resin(Amberlite IR-400 manufactured by Rhom & Haas Co.) to prepare watercontaining not more than 3 mg/l of calcium ion and magnesium ion. To thewater thus-treated were added sodium dichloroisocyanurate in an amountof 20 mg/l and sodium sulfate in an amount of 0.05 g/l. The pH of thesolution was in a range from 6.5 to 7.5.

    ______________________________________                                        Stabilizing Solution:                                                         ______________________________________                                        Formalin (37%)           2.0     ml                                           Polyoxyethylene-p-monononylphenylether                                                                 0.3     g                                            (average degree of polymerization: 10)                                        Disodium ethylenediaminetetraacetate                                                                   0.05    g                                            Water to make            1.0     l                                            pH                       5.0 to 8.0                                           ______________________________________                                    

Each of the samples thus processed was subjected to sensitometry. Theresults obtained are shown in Table 5 below.

                  TABLE 5                                                         ______________________________________                                                                       Gra-  Maximum                                                       Sensitivity                                                                             dation                                                                              Density                                  Sample                                                                              Coupler        (s)*      (Υ)**                                                                       (Dm)                                     ______________________________________                                        5A-1   (7)           90        2.75  2.72                                           (Present Invention)                                                     5A-2  (12)           85        2.82  2.80                                           (Present Invention)                                                     5A-3  (24)           83        2.89  2.82                                           (Present Invention)                                                     5A-4  (27)           87        2.80  2.74                                           (Present Invention)                                                     5A-5  (31)           91        2.73  2.70                                           (Present Invention)                                                     5A-6  (36)           82        2.90  2.85                                           (Present Invention)                                                     5A-7  (41)           80        2.91  2.86                                           (Present Invention)                                                     5B-1  Comparative    100       2.56  2.64                                           Coupler (M-3)                                                           5B-2  Comparative    109       2.52  2.53                                           Coupler (M-4)                                                           5B-3  Comparative    110       2.54  2.52                                           Coupler (M-5)                                                           ______________________________________                                         *Sensitivity (s) is a value of the exposure amount necessary for providin     a density of fog plus 0.5 and shown relatively taking the value of            Comparative Sample (5B1) as 100.                                              **Gradation (Υ) means a slope of a sensitometric curve between a      point having a density of 0.5 and a point having a density of 2.5.       

From the results shown in table 5, it can be seen that the magentacouplers according to the present invention exhibit high sensitivity andexcellent color forming property due to the reduced interaction withsilver in comparison with the comparative couplers.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A magenta image forming method which comprisesdeveloping a silver halide photographic material with a developingsolution containing an aromatic primary amine developing agent in thepresence of an imidazo(1,2-b)-pyrazole type coupler represented by thefollowing general formula (I): ##STR21## wherein R₁ represents ahydrogen atom, an alkyl group, an alkoxy group, an aryloxy group or anaryl group; R₂ represents an alkoxy group, an aryloxy group or asubstituted or unsubstituted amino group represented by the followingformula: ##STR22## wherein R' and R", which may be the same ordifferent, each represents a hydrogen atom, or an aryl group, or R' andR" may combine with each other to form a ring; R₃ represents an alkylgroup or an aryl group; and X represents a halogen atom or a groupbonded to the coupling position through a sulfur atom.
 2. The imageforming method as claimed in claim 1, wherein the coupler represented bygeneral formula (I) is incorporated into a light-sensitive material. 3.The image forming method as claimed in claim 2, wherein the amount ofthe coupler represented by general formula (I) is 1×10³ to 1 mol per molof silver.
 4. The image forming method as claimed in claim 1, whereinthe coupler represented by general formula (I) is incorporated into adeveloping solution.
 5. The image forming method as claimed in claim 4,wherein the amount of the coupler represented by general formula (I) isfrom 1 to 6 grams per liter of developing solution.
 6. A silver halidecolor photographic material comprising a support having thereon at leastone green-sensitive layer containing an imidazo(1,2-b)pyrazole typecoupler represented by the following general formula (I): ##STR23##wherein R₁ represents a hydrogen atom, an alkyl group, an alkoxy group,an aryloxy group or an aryl group; R₂ represents an alkoxy group, anaryloxy group or a substituted or unsubstituted amino group representedby the following formula: ##STR24## wherein R' and R", which may be thesame or different, each represents a hydrogen atom, or an aryl group, orR' and R" may combine with each other to form a ring; R₃ represents analkyl group or an aryl group; and X represents a halogen atom or a groupbonded to the coupling position through a sulfur atom.
 7. The silverhalide color photographic material as claimed in claim 6, wherein R₁ isa substituent having a Hammett's σ_(p) value of not more than 0.1. 8.The silver halide color photographic material as claimed in claim 7,wherein the Hammett's σ_(p) value is in the range of -0.5 to 0.05. 9.The silver halide color photographic material as claimed in claim 6,wherein R₁ is an alkyl group, an aryloxy group or an alkoxy group. 10.The silver halide color photographic material as claimed in claim 6,wherein R₂ is an alkoxy group or a substituted amino group.
 11. Thesilver halide color photographic material as claimed in claim 6, whereinthe imidazo[1,2-b]-pyrazole type coupler is a copolymer composed of avinyl monomer containing a coupler moiety represented by general formula(I) and a non-color forming ethylenic monomer which does not couple withan oxidation product of an aromatic primary amine developing agent. 12.The silver halide color photographic material as claimed in claim 11,wherein the non-color forming ethylenic monomers which do not couplewith the oxidation products of aromatic primary amine developing agentsare selected form the group consisting of acrylic acid, an ester derivedfrom an acrylic acid, an amide derived from an acrylic acid, methylenedibisacrylamide, vinyl ester, acrylonitrile, methacrylonitrile, anaromatic vinyl compound, itaconic acid, citraconic acid, crotonic acid,vinylidene chloride, vinyl alkyl ether, maleic acid, maleic anhydride,an ester of maleic acid, N-vinyl-2-pyrrolidone, N-vinyl pyridine,2-vinyl pyridine and 4-vinyl pyridine.
 13. The silver halide colorphotographic material as claimed in claim 6, wherein the layercontaining the imidazo[1,2-b]pyrazole type coupler is a green-sensitivesilver halide emulsion layer.
 14. The silver halide color photographicmaterial as claimed in claim 13, wherein the silver halide colorphotographic material further comprises at least one red-sensitivesilver halide emulsion layer containing a cyan coupler and at least oneblue-sensitive silver halide emulsion layer containing a yellow coupler.15. The silver halide color photographic material as claimed in claim 6,wherein the alkyl group is a substituted or unsubstituted straight chainor branched chain alkyl group having from 1 to 32 carbon atoms.
 16. Thesilver halide color photographic material as claimed in claim 6, whereinthe alkoxy group is a group composed of a substituted or unsubstituted,straight chain or branched chain alkyl group having from 1 to 32 carbonatoms bonded to an oxygen atom and the alkyl moiety of the alkoxy groupmay be substituted.
 17. The silver halide color photographic material asclaimed in claim 6, wherein the aryloxy group is an unsubstitutedphenoxy or naphthyloxy group or a substituted phenoxy or naphthyloxygroup.
 18. The silver halide color photographic material as claimed inclaim 6, wherein the aryl group is an unsubstituted phenyl or naphthylgroup or a substituted phenyl or naphthyl group wherein the substituentgroups have a Hammett's value of not more than 0.